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Biomedical subjects

E Block

Publications and source records attributed to E Block.

At least 19 recordsLinked to original sources
PubMed2006

Prediction and evaluation of urine and urinary nitrogen and mineral excretion from dairy cattle.

Urine excretion is a substantial factor in the amount of manure that needs to be managed, and urinary N can contribute to ammonia volatilization. Development and validation of prediction equations focusing on dietary factors to decrease urine and urinary nutrient excretion will provide information for managing urine and feces separately or for other future technologies. The objective of this study was to develop equations for prediction of urine excretion and excretion of urinary N, Na, and K and to evaluate both new and previously published prediction equations for estimation of urine and urinary nutrient excretion from lactating dairy cows. Data sets from metabolism studies conducted at Washington State University were compiled and evaluated for excretion of minerals. Urine excretion averaged 24.1 kg/d and urinary nitrogen excretion ranged from 63 to 499 g/d in the calibration data set. Regression equations were developed to predict urine excretion, urinary N excretion, and urinary Na and K excretion. Predictors used in the regression equations included milk yield, body weight, dietary crude protein percentage, milk urea nitrogen, and nutrient intakes. Previously published prediction equations were evaluated using data sets from Washington State University and the University of Wisconsin. Mean and linear biases were evaluated by determining the regression of residuals on predicted values. Evaluation and validation of prediction equations are important to develop equations that will more accurately estimate urine and urinary nitrogen excretion from lactating dairy cows.

Animal Nutritional Physiological Phenomena↗
PubMed2006

Hypocalcemia in dairy cows: meta-analysis and dietary cation anion difference theory revisited.

Data from 137 published trials involving 2,545 calvings were analyzed using random effects normal logistic regression models to identify risk factors for clinical hypocalcemia in dairy cows. The aim of the study was to examine which form, if any, of the dietary cation anion difference (DCAD) equation provided the best estimate of milk fever risk and to clarify roles of calcium, magnesium, and phosphorus concentrations of prepartum diets in the pathogenesis of milk fever. Two statistically equivalent and biologically plausible models were developed that predict incidence of milk fever. These models were validated using data from 37 trials excluded from the original data used to generate the models; missing variables were replaced with mean values from the analyzed data. The preferred models differed slightly; Model 1 included prepartum DCAD, and Model 2 included prepartum dietary concentrations of potassium and sulfur alone, but not sodium and chloride. Other factors, included in both models were prepartum dietary concentrations of calcium, magnesium, phosphorus; days exposed to the prepartum diet; and breed. Jersey cows were at 2.25 times higher risk of milk fever than Holstein cows in Model 1. The results support the DCAD theory of greater risk of milk fever with higher prepartum dietary DCAD (odds ratio = 1.015). The only DCAD equation supported in statistical analyses was (Na(+) + K(+)) - (Cl(-) + S(2-)). This finding highlights the difference between developing equations to predict DCAD and those to predict milk fever. The results support a hypothesis of a quadratic role for Ca in the pathogenesis of milk fever (model 1, odds ratio = 0.131; Model 2, odds ratio = 0.115). Milk fever risk was highest with a prepartum dietary concentration of 1.35% calcium. Increasing prepartum dietary magnesium concentrations had the largest effect on decreasing incidence of milk fever in both Model 1 (odds ratio = 0.006) and Model 2 (odds ratio = 0.001). Increasing dietary phosphorus concentrations prepartum increased the risk of milk fever (Model 1, odds ratio = 6.376; Model 2, odds ratio = 9.872). The models presented provide the basis for the formulation of diets to reduce the risk of milk fever and strongly support the need to evaluate macro mineral nutrition apart from DCAD of the diet.

Animals↗
PubMed2005

Effects of BioChlor and Fermenten on microbial protein synthesis in continuous culture fermenters.

Meta analysis models were constructed from a data-set of 15 continuous culture fermenter trials and 118 observations on studies with either BioChlor (n = 23 observations) or Fermenten (n = 95) included at 10 and 3%, respectively, of dietary dry matter (DM) to evaluate effects of the ingredients BioChlor and Fermenten (B/F) on rumen function. Digestibility of crude protein was significantly increased by 11% with B/F treatment. This was reflected in significant increases in digestibility of DM and organic matter (OM) by 3.6 and 7.9%, respectively. Increased amounts of sugar in the diet in the presence of B/F tended to reduce digestibility of non-structural carbohydrates (NSC); however, the net effect on NSC digestion was small. There was no effect of treatment on most individual volatile fatty acids (VFA) or total VFA production. Propionate production, however, was significantly reduced in treated fermenters. The main effect of B/F as well as of starch and soluble fiber when combined with the treatment was to increase propionate production; however, the interaction between B/F treatment and sugar decreased propionate production markedly, resulting in a net decrease. The acetate-to-propionate ratio increased by 6% with B/F, largely as a result of the decrease in propionate. Production of nonammonia nitrogen was 1% less in B/F-treated fermenters, and interactions between treatment and starch, sugar, or soluble fiber were significant. Treated fermenters produced 15.7% more microbial nitrogen, in association with a significant 37% increase in rumen protein digestion. Interactions between treatment and starch, soluble fiber, or sugar influenced these results. The interaction of B/F and sugar resulted in a decrease in undegradable protein N and an increase in microbial nitrogen production. Ammonia nitrogen concentrations were increased by 24.6% in treated fermenters. Efficiency of microbial nitrogen production from DM, OM, or carbohydrate was significantly increased by B/F. Sugar content increased efficiency of microbial protein production/kg of OM digested or carbohydrate digested in the presence of treatment by >10 times the increase that was attributable to the interaction of treatment with starch. Treatment with B/F reduced moles of VFA produced/kg of microbial nitrogen produced by 16%. This effect was also substantially influenced by interactions between B/F and sugar. If the fermenter results are representative of those in vivo, milk production responses to treatment with B/F will depend on amounts of starch, soluble fiber, and, particularly, sugar in diets. Milk production responses will also depend on the quality of protein in the diet and the comparative benefit that increased flux of microbial nitrogen provides. Increased digestibility of OM should allow additional ruminant production benefits.

Amino Acids↗
PubMed2005

Prediction of manure and nutrient excretion from dairy cattle.

Accurate estimates of manure excretion are needed for planning manure storage facilities and for nutrient management. Data sets from metabolism studies conducted at several universities were compiled and evaluated for excretion of total manure, N, P, and K. Animal groups included calves weighing up to 204 kg, heifers weighing between 274 and 613 kg, nonlactating cows, and lactating cows. Regression equations were developed to predict excretion of total manure, total dry matter, N, P, and K. Predictors used in the regression equations for lactating cows included milk yield, percentages of protein and fat in milk, dietary concentrations of crude protein and neutral detergent fiber, and intakes of nutrients. The regression equations provide improved predictions of excretion and enable more accurate planning of manure storage and nutrients to be managed at the farm level.

Animal Nutritional Physiological Phenomena↗
PubMed2004

Blood melatonin and prolactin concentrations in dairy cows exposed to 60 Hz electric and magnetic fields during 8 h photoperiods.

Two experiments were conducted to test the hypothesis that electric and magnetic field (EMF) exposure may result in endocrine responses similar to those observed in animals exposed to long days. In the first experiment, 16 lactating, pregnant Holstein cows were assigned to two replicates according to a crossover design with treatment switchback. All animals were confined to wooden metabolic cages and maintained under short day photoperiods (8 h light/16 h dark). Treated animals were exposed to a vertical electric field of 10 kV/m and a horizontal magnetic field of 30 microT (EMF) for 16 h/day for 4 weeks. In a second, similar experiment, 16 nonlactating, nonpregnant Holstein cows subjected to short days were exposed to EMF, using a similar protocol, for periods corresponding to the duration of one estrous cycle. In the first experiment, circulating MLT concentrations during the light period showed a small numerical decrease during EMF exposure (P < .05). Least-square means for the 8 h light period were 9.9 versus 12.4 pg/ml, SE = 1.3. Melatonin concentrations during the dark period were not affected by the treatment. A similar trend was observed in the second experiment, where MLT concentrations during the light period tended to be lower (8.8 pg/ml vs. 16.3 pg/ml, P < .06) in the EMF exposed group, and no effects were observed during the dark period. Plasma prolactin (PRL) was increased in the EMF exposed group (16.6 vs. 12.7 ng/ml, P < .02) in the first experiment. In the second experiment, the overall PRL concentrations found were lower, and the mean plasma PRL concentration was not affected by treatment. These experiments provide evidence that EMF exposure may modify the response of dairy cows to photoperiod.

Animals↗
PubMed2004

Ruminal biohydrogenation in Holstein cows fed soybean fatty acids as amides or calcium salts.

Fatty amides of high oleate fats and calcium salts of palm oil were reported to resist biohydrogenation by ruminal microorganisms. This study was conducted to determine whether converting polyunsaturated fat sources to amides and calcium salts had equal ability to resist biohydrogenation. A total mixed ration consisting of forage and concentrate contained (dry basis): 1) 2.45% soybean oil (SBO), 2) 2.75% calcium salt of SBO, 3) 2.75% amide of SBO, or 4) 2.75% of a mixture of the calcium salt and amide (80:20, wt/wt) of SBO. The 4 diets were fed ad libitum to 4 multiparous lactating Holstein cows fitted with ruminal cannulas in a 4 x 4 Latin square with 21-d periods. Omasal samples were taken to measure postruminal fatty acid content and determine the extent of ruminal biohydrogenation. Adding SBO to the diets as either calcium salts or amides increased omasal flow of C18:2 (n-6) from 25 to 39 g/d. Omasal flow of C18:1 increased from 36 to 49 g/d when SBO was fed to cows as calcium salts, but increased to 86 g/d when SBO was fed as amides. Adding the soybean amide to the diet more than doubled the delivery of C18:1 (n-9) to the omasum of lactating cows, but it also increased trans fatty acid production in the rumen accompanied by milk fat depression. In this study, calcium salts and amide derivatives of fatty acids were both effective in enhancing omasal flow of unsaturataed fatty acids in lactating dairy cows. Amides were more effective than calcium salts for increasing the postruminal flow of oleic acid.

Amides↗
PubMed2003

Responses of the estrous cycle in dairy cows exposed to electric and magnetic fields (60 Hz) during 8-h photoperiods.

To study the effects of exposure to extremely low frequency (ELF) electric and magnetic fields (EMF) on the estrous cycle of dairy cows under short-day photoperiod, 16 non-lactating, non-pregnant Holstein cows were exposed to a vertical electric field of 10 kV/m and a horizontal magnetic field of 30 microT for 16 h per day in a cross-over design consisting of two sequences. Each sequence included three periods, and each period corresponded to the duration of one estrous cycle. All animals were maintained under short photoperiod (8 h light/16 h dark) during the trial. Exposure to EMF had an impact on the duration of a complete estrous cycle (P<0.01) and on the duration of the luteal phase (P<0.01). The mean duration of one cycle was 19.5+/-0.4 for the control and 21.3+/-0.4 days for the exposed animals, respectively. The mean duration of the luteal phase was 15.4+/-0.4 days for the control and 17.2+/-0.4 days for the exposed group. The total area under the progesterone (P(4)) curve, the amplitude of the curve or the slope of the P(4) rise at the onset of the luteal phase were not affected by EMF exposure. Results indicate that exposure to EMF may increase the duration of the estrous cycle.

Animals↗
PubMed2003

Direct-fed microbial supplementation on the performance of dairy cattle during the transition period.

The influence of a direct-fed microbial (DFM) on the prepartum period and the effects on production performance during the postpartum period was investigated using 64 multiparous Holstein cows. Two close-up dry cow diets were fed to two groups of 32 cows each starting 21 d precalving as follows: 1) no DFM and 2) DFM. Post-calving cows were fed a lactation ration with or without DFM supplementation.The direct-fed microbial (DFM) supplement contained 2 × 109 viable yeast cells and 5 × 109 cfu of bacteria (Enterococcus faecium) per cow per day, top dressed in a 90-g supplement [corrected].The DMI during the prepartum period was not affected by DFM supplementation. During the postpartum period, DMI, milk yield, and milk protein content were higher for cows receiving DFM supplementation compared with no DFM. Blood glucose and insulin levels were higher and NEFA levels were lower for cows receiving DFM during the postpartum period. These data suggest that targeted DFM supplementation increased DMI and milk production postpartum. Blood metabolite information would suggest this response was associated with more glucose being made available and less fatty acids being mobilized from lipid stores.

Animals↗
PubMed2002

Effects of insulin, recombinant bovine somatotropin, and their interaction on insulin-like growth factor-I secretion and milk protein production in dairy cows.

This trial was designed to test the effects of insulin, recombinant bovine somatotropin (rbST), and their interaction on milk protein and selected blood parameters in dairy cows. Eight Holstein cows (86 +/- 10 d in milk) were divided in two groups and used in two replicates of a Latin square design with four animals, four periods, and four treatments: 1) intravenous infusion of saline, 2) infusion of saline and subcutaneous administration of 40 mg of rbST per day, 3) intravenous infusion of 12 mg of insulin per day coupled with glucose infusion, and 4) rbST administration combined with insulin and glucose infusion. The glucose infusion rate was adjusted to maintain euglycemia. Each experimental period lasted 14 d: treatments were administered during the first 6 d, and no treatment was administered during the following 8-d resting phase. The average daily amount of glucose infusion needed to avoid hypoglycemia was 2.8 kg/cow when only insulin was infused as opposed to 2.2 kg/cow when both insulin and rbST were administered, indicating that either rbST causes a peripheral resistance to insulin or rbST increased liver gluconeogenesis or both. Data from the last 3 d of infusion were analyzed by using the SAS system for mixed models. Percent protein of milk tended to be lower (2.84 vs. 2.79%) and milk urea content was lower (16.6 vs. 14.8 mg/dl) during rbST administration, regardless of insulin infusion. Insulin infusion increased percent protein (2.78 vs. 2.85%) and percent casein (2.36 vs. 2.46%) and decreased milk urea content (17.1 vs. 14.3 mg/dl) regardless of rbST administration. For milk yield, protein yield, casein yield, lactose percent, and lactose yield, there were significant interactions between insulin and rbST administration. For example, casein yield averaged 1.17, 1.12, 1.20, and 1.28 kg/d for saline, insulin, rbST, and insulin combined with rbST, respectively. Similarly, there was a significant interaction between insulin and rbST on IGF-I levels, which were 122.5, 181.3, 342.3, and 492.2 ng/ml for saline, insulin, rbST, and insulin combined with rbST, respectively. In conclusion, these results clearly demonstrated that insulin interacts with bST in early lactation to improve milk protein synthesis and yield in dairy cows. These effects are probably mediated through a combination of bST nutrient mobilization, bST-induced gluconeogenesis, bST-induced insulin peripheral resistance, and bST/insulin synergism on insulin-like growth factor-I secretion and on mammary epithelial tissue.

Animal Nutritional Physiological Phenomena↗
PubMed2002

Effect of electric and magnetic fields (60 Hz) on production, and levels of growth hormone and insulin-like growth factor 1, in lactating, pregnant cows subjected to short days.

Electric and magnetic fields (EMF) are generated by the transmission of electricity through high tension lines traversing rural areas. Previous studies showed increased dry matter intake (DMI) and fat corrected milk in dairy cows exposed to EMF. Because EMF exposure has been shown to suppress pineal release of melatonin in some species, it was hypothesized that EMF effects resemble those of exposure to long days. Previous studies have shown that DMI and milk production increase in dairy cattle in response to long day photoperiods, and this has been observed in association with increased circulating insulin-like growth factor 1 (IGF-1), but not growth hormone (GH). The hypothesis that EMF act by modifying the response to photoperiod was tested by subjecting dairy cows to controlled EMF exposure while keeping them under short-day conditions. Sixteen lactating, pregnant Holstein cows were exposed to a vertical electric field of 10 kV/m and a horizontal magnetic field of 30 microT in a crossover design with treatment switchback. Two groups of eight cows each were exposed to EMF for 16 h/d in either oftwo sequences. Each sequence consisted of three consecutive 28-d periods. All animals were maintained under short day conditions (8 h light, 16 h dark) during the trial. DMI and plasma IGF-1 were increased (P < 0.01) during EMF exposure (17.03 vs.16.04 kg/d, SE = 0.4; 137 +/- 6 ng/ml vs 126 +/- 6, respectively). The mean GH concentration was not affected, but a treatment x hour interaction was detected, with GH lower for the EMF exposed animals during the first 16 h of the sampling period, and higher for the last 8 h. Overall, the yield of milk or its components was not affected by EMF exposure, but milk yield was significantly higher for the exposed animals during wk 4 of treatment.

Animals↗
PubMed2001

Changes in the practice of percutaneous coronary intervention: a comparison of enrollment waves in the National Heart, Lung, and Blood Institute (NHLBI) Dynamic Registry.

The National Heart, Lung, and Blood Institute Dynamic Registry includes 15 clinical sites in wave 1, and 16 sites in wave 2 as well as a data-coordinating center. The first wave of enrollment began in July 1997 and was completed in February 1998. The second wave began in February 1999 and ended in June 1999. There were a total of 2,526 patients in wave 1 and 2,109 patients in wave 2. Comprehensive pre-, intra-, and postprocedure (in-hospital) data were analyzed for changes between recruitment waves. Patients in wave 2 were more frequently nonwhite (p < or = 0.001), hypertensive by history (p < or = 0.001), had more significant noncardiac comorbidity (p < or = 0.01), and had more frequently undergone prior percutaneous coronary intervention (p < 0.05). Patients in wave 2 underwent percutaneous coronary intervention in a setting of acute coronary syndromes more frequently than wave 1 patients (p < or = 0.001). However, most interventions in both waves were performed on 1 vessel, irrespective of the extent of disease. Attempted lesions in wave 2 were longer (p < or = 0.001), less frequently totally occluded (p < or = 0.001), and more frequently in vessels with a prior stent (p < or = 0.01). Using the American Heart Association/American College of Cardiology lesion classification scheme, attempted lesions in wave 2 were less complex than those in wave 1 (p < or = 0.001). Stent use increased significantly from wave 1 (67%) to wave 2 (79%, p < or = 0.001) as did the use of platelet glycoprotein IIb/IIIa antagonists (wave 1, 24%; wave 2, 32%: p < 0.001). Procedural outcomes (angiographic success without major in-hospital adverse events) were excellent in both waves 1 (94.6%) and 2 (95.6%) and were not significantly different. However, the frequency of significant procedural coronary dissection and in- and out-of-laboratory abrupt closure were significantly less in wave 2 (p < or = 0.001) Discharge medications were more likely to include angiotensin-converting enzyme inhibitors, beta-adrenergic blocking agents, and hypolipidemic treatment in wave 2 than in wave 1 (p < or = 0.001). These data indicate a continuing aggressive approach to patient care over the time interval analyzed. Although overall procedural outcomes are excellent, procedural safety has been further enhanced. There is also a growing awareness of the importance of secondary prevention among interventional cardiologists.

Aged↗
PubMed2001

Characterization of the biological activity of gamma-glutamyl-Se-methylselenocysteine: a novel, naturally occurring anticancer agent from garlic.

Gamma-glutamyl-Se-methylselenocysteine (GGMSC) has recently been identified as the major Se compound in natural garlic and selenized garlic. Our working hypothesis is that GGMSC serves primarily as a carrier of Se-methylselenocysteine (MSC), which has been demonstrated in past research to be a potent cancer chemopreventive agent in animal carcinogenesis bioassays. The present study was designed to examine the in vivo responses to GGMSC or MSC using a variety of biochemical and biological end points, including (a) urinary Se excretion as a function of bolus dose; (b) tissue Se accumulation profile; (c) anticancer efficacy; and (d) gene expression changes as determined by cDNA array analysis. Our results showed that like MSC, GGMSC was well absorbed p.o., with urinary excretion as the major route for eliminating excess Se. When fed chronically, the profile of Se accumulation in various tissues was very comparable after treatment with either GGMSC or MSC. In rats that had been challenged with a carcinogen, supplementation with either GGMSC or MSC resulted in a lower prevalence of premalignant lesions in the mammary gland, and fewer mammary carcinomas when these early lesions were allowed to progress. More importantly, we found that a short term GGMSC/MSC treatment schedule of 4 weeks immediately after carcinogen dosing was sufficient to provide significant cancer protection, even in the absence of a sustained exposure past the initial 4-week period. With the use of the Clontech Atlas Rat cDNA Array, we further discovered that the gene expression changes induced in mammary epithelial cells of rats that were given either GGMSC or MSC showed a high degree of concordance. On the basis of the collective biology, biochemistry, and molecular biology data, we conclude that GGMSC is an effective anticancer agent with a mechanism of action very similar to that of MSC.

Animals↗
PubMed2001

Drug absorption in vitro model: filter-immobilized artificial membranes. 2. Studies of the permeability properties of lactones in Piper methysticum Forst.

The assessment of transport properties of 23 drug and natural product molecules was made using the in vitro model based on filter-immobilized artificial membranes (filter-IAM), assembled from phosphatidylcholine in dodecane, in buffer solutions at pH 7.4. Five of the compounds were lactones extracted from the roots of the kava-kava plant. Experiments were designed to test the effects of stirring (0-600 rpm) during assays and the effects of varying the assay times (2-15 h). The highly mobile kava lactones permeated in the order dihydromethisticin (40)>yangonin (37)>kavain (34)>methisticin (32)>desmethoxyyangonin (26), the numbers in parentheses being the measured effective permeabilities in units of 10(-6) cm/s. By comparison, commercial drugs ranked: phenazopyridine (35)>testosterone (19)>propranolol (13)>ketoconazole (6.3)>piroxicam (2.2)>caffeine (1.7)>metoprolol (0.8)>terbutaline (0.01). In addition to permeability measurements, membrane retention of compounds was determined. Yangonin, desmethoxyyangonin, ketoconazole, and phenazopyridine were more than 60% retained by the artificial membranes containing phospholipids. Stirring during assay significantly increased the observed permeabilities for highly mobile molecules, but had minimal impact on the poorly permeable molecules. The influence of hydrogen bonding was explored by determining permeabilities using filters coated with dodecane free of phospholipids. In the filter-IAM method, concentrations were determined by microtitre plate UV spectrophotometry and by LC-MS. Higher-throughput was achieved with direct UV by the use of 96-well microtitre plate formats and with LC-MS by the use of cassette dosing (five-in-one).

Absorption↗
PubMed2001

Allium chemistry: synthesis, natural occurrence, biological activity, and chemistry of Se-alk(en)ylselenocysteines and their gamma-glutamyl derivatives and oxidation products.

Syntheses are reported for gamma-glutamyl Se-methylselenocysteine (Sa), selenolanthionine (16), Se-1-propenylselenocysteine (Gd), Se-2-methyl-2-propenyl-L-selenocysteine (6e), and Se-2-propynyl-L-selenocysteine (6f). Oxidation of 8a and Se-methylselenocysteine (Ga) gives methaneseleninic acid (24), characterized by X-ray crystallography, and dimethyl diselenide (25). Oxidation of Se-2-propenyl-L-selenocysteine (6c) gives allyl alcohol and 3-seleninoalanine (22). Compound 22 is also formed on oxidation of 16 and selenocystine (4). Oxidation of 6d gives 2-[(E,Z)-1-propenylseleno]propanal (36). These oxidations occur by way of selenoxides, detected by chromatographic and spectroscopic methods. The natural occurrence of many of the Se-alk(en)ylselenocysteines and their gamma-glutamyl derivatives and oxidation products is discussed. Three homologues of the potent cancer chemoprevention agents 6a and 6c, namely 6d-f, were evaluated for effects on cell growth, induction of apoptosis, and DNA-damaging activity using two murine mammary epithelial cell lines. Although each compound displays a unique profile of activity, none of these compounds (Gd-f) is likely to exceed the chemopreventive efficacy of selenocysteine Se-conjugates Ga and 6c.

Allium↗
PubMed2000

Reduction of permanganate by thioanisole: lewis acid catalysis

The oxidation of sulfides and sulfoxides by permanganate in anhydrous acetone solutions is catalyzed by Lewis acids such as iron(III) chloride, zinc chloride, and mercury(II) chloride. The reaction kinetics unequivocally confirm that the function of these catalysts is to activate the oxidant by forming permanganate/Lewis acid complexes analogous to the protonation of Mn by Bronsted acids. A Hammett analysis of the rate constants for the oxidation of a series of substituted thioanisoles gives a negative rho value (-1. 11) indicative of an electron deficient transition state. No secondary kinetic isotope effect is observed when the hydrogens of the methyl group are replaced by deuterium. Despite previous observations that sulfoxides are preferentially oxidized in competitive experiments, sulfides are oxidized more rapidly when individual rates are measured. All of these observations are most consistent with a mechanism in which the reductant reacts with the oxidant via initial ligation.

Journal Article↗
PubMed2000

High-performance liquid chromatography of selenium compounds utilizing perfluorinated carboxylic acid ion-pairing agents and inductively coupled plasma and electrospray ionization mass spectrometric detection.

Increasing speciation demands in clinical chemistry, toxicology and nutrition have made the determination of the total elements in a sample inadequate; the amount of an element and the chemical forms in which it is present need to be known. Inductively coupled plasma mass spectrometry (ICP-MS) was used after high-performance liquid chromatographic (HPLC) separation, as was electrospray ionization mass spectrometry (ESI-MS). The effect of variation of the number of carbon atoms in perfluorinated carboxylic acids used as ion-pairing agents for the separation of selenium compounds was examined. Trifluoroacetic acid (0.1%), pentafluoropropanoic acid (0.1%) or heptafluorobutanoic acid (0.1%; HFBA) were alternatively used as additives to methanol-water (1:99, v/v) solutions as mobile phases. Reversed-phase HPLC-ICP-MS with 0.1% HFBA in the mobile phase allowed more than 20 selenium compounds to be separated in 70 min in an isocratic elution mode; the separation of natural selenium-enriched sample extracts was examined and explained. The pH of the 0.1% HFBA solution was modified with hydrochloric acid or ammonia and the pH of the sample extracts before injection was modified in order to overcome unwanted double peak formation in the chromatograms of sample extracts. Oxidations of standard gamma-glutamyl-Se-methylselenocysteine and Se-methylselenocysteine were carried out using 30% H2O2 solution and identifications of selenium-containing oxidation products were made using HPLC-ICP-MS and HPLC-ESI-MS. The principal organic oxidation product in both cases was methaneseleninic acid (MeSeO2H).

Carboxylic Acids↗
PubMed2000

Chemical speciation influences comparative activity of selenium-enriched garlic and yeast in mammary cancer prevention.

A recent human intervention trial showed that daily supplementation with selenized yeast (Se-yeast) led to a decrease in the overall cancer morbidity and mortality by nearly 50%; past research has also demonstrated that selenized garlic (Se-garlic) is very effective in mammary cancer chemoprevention in the rat model. The goal of this study was to compare certain biological activities of Se-garlic and Se-yeast and to elucidate the differences based on the chemical forms of selenium found in these two natural products. Characterization of organic selenium compounds in yeast (1922 microg/g Se) and garlic (296 microg/g Se) was carried out by high-performance liquid chromatography with inductively coupled plasma mass spectrometry or with electrospray mass spectrometry. Analytical speciation studies showed that the bulk of the selenium in Se-garlic and Se-yeast is in the form of gamma-glutamyl-Se-methylselenocysteine (73%) and selenomethionine (85%), respectively. The above methodology has the sensitivity and capability to account for >90% of total selenium. In the rat feeding studies, supplementation of Se-garlic in the diet at different levels consistently caused a lower total tissue selenium accumulation when compared to Se-yeast. On the other hand, Se-garlic was significantly more effective in suppressing the development of premalignant lesions and the formation of adenocarcinomas in the mammary gland of carcinogen-treated rats. Given the present finding on the identity of selenomethionine and gamma-glutamyl-Se-methylselenocysteine as the major form of selenium in Se-yeast and Se-garlic, respectively, the metabolism of these two compounds is discussed in an attempt to elucidate how their disposition in tissues might account for the differences in cancer chemopreventive activity.

Adenocarcinoma↗